Silica pigments and preparation thereof

ABSTRACT

Silica pigments are precipitated by the acidulation of aqueous sodium silicate solution with carbon dioxide, and for controlling the characteristics of the silica pigment obtained, as evidence by the physical properties imparted to rubber vulcanizates thereby when used as a rubber reinforcing filler, the silicate solution is maintained at different average temperatures during different stages of such acidulation, which end respectively, with the appearance of a Tyndall effect, the subsequent precipitation of at least 10 percent of the silica, the subsequent precipitation to at least 90 percent of the silica, and the final neutralization and flocking of the precipitate.

States atent Burke, Jr. 1 March 6, 1973 [5 SILICA PIGMENTS AND 3,307,906 3/1967 Burke, Jr ..23/182 PREPARA THEREOF 3,325,249 6/1967 Burke, Jr ..23/ 182 3,337,299 8/1967 Burke, Jr ..23/182 [76] Invenm Burke 3,503,707 3/1970 Burke, Jr ..23/182 1266, Pampano Beach, Fla. 2,601,235 6/1952 Alexander et a1. ..23/182 [22] Filed: Oct. 3, 1969 Primary ExaminerEdward Stern [21] Appl' NO: 864,954 Att0rneyl'lall & Houghton, John W. Behringer, Eu-

Related US. Application Data [52] US. Cl. ..423/339, 423/421, 106/288 B, 106/308 M, 260/415 [51] Int. Cl.....C0lb 33/00, COlb 33/14, COlb 33/18 [58] Field of Search ..23/182, 110 R, 110 A, 63; 423/339, 421

[56] References Cited UNITED STATES PATENTS 2,940,830 6/1960 Thornhill ..23/182 3,085,861 4/1963 Thornhill et a1 ....23/l82 3,172,726 3/1965 Burke, Jr. et a1. ....23/182 3,172,727 3/1965 Burke, Jr. et al..... ....23/l82 3,250,594 5/1966 Burke, Jr. et al. ....23/l82 3,281,210 10/1966 Burke, Jr. et a1. ..23/182 gene L. Bernard, Martin J. Brown, James N. Dresser, W! Brown Morton, Jr., John T. Roberts and Malcolm L. Sutherland Silica pigments are precipitated by the acidulation of aqueous sodium silicate solution with carbon dioxide, and for controlling the characteristics of the silica pigment obtained, as evidence by the physical properties imparted to rubber vulcanizates thereby when used as a rubber reinforcing filler, the silicate solution is maintained at different average temperatures during different stages of such acidulation, which end respectively, with the appearance of a Tyndall effect, the subsequent precipitation of at least 10 percent of the silica, the subsequent precipitation to at least 90 percent of the silica, and the final neutralization and flocking of the precipitate.

ABSTRACT 7 Claims, No Drawings SILICA PIGMENTS AND PREPARATION THEREOF CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of application Ser. No. 698,358 filed Jan. 16, 1968, now abandoned, itself a continuation of application Ser. No. 480,143 filed Aug. 16, 1965 (now abandoned).

This invention relates to silica pigment materials and to the preparation thereof from aqueous alkali metal silicate, and aims generally to improve the same.

OBJECTS Particular objects of the present invention, severally and interdependently, are to provide an improved process for the preparation of silica pigments; to provide a process for controlling the relative sizes of the primary particles of colloidal silica and of the aggregates and fiocs thereof which form the silica pigment particles, e.g. for the production of improved silica pigment materials; and to provide improved silica pigments having useful characteristics and at an economical cost.

Other objects and advantages of the invention will be apparent from a consideration of the herein set 'forth general and specific descriptions of illustrative embodiments thereof.

The invention resides in the new and useful features and combinations characterizing the process and products herein exemplified, and is more particularly defined in the appended claims.

GENERAL DESCRIPTION The present invention is concerned with the production of silica pigment by the acidulation of aqueous alkali metal silicate e.g., sodium silicate, especially with carbon dioxide as acidulating agent.

The course of the acidulation of sodium silicate solution to precipitate silica therefrom according to known processes such as those set forth in my copending joint applications Ser. No. 422,144 (now U.S. Pat. No. 3,250,594). Ser. No. 422,454 can be classified in several distinct stages. Prior to acidulation, of course, is the preparatory stage in which the sodium silicate is diluted with water and in which the factor x designating the weight ratio of Si to Na 0 in the sodium silicate formula Na 0/(Si0 remains unchanged. As a practical matter, in commercial sodium silicate used for the production of precipitated silica, the value of x lies below 3.8, usually in the range of about 3.0 to 3.4, e.g., 3.22 in the 4 l Be sodium silicate of commerce.

The first period or stage in such known processes of acidulation one can call the pre-precipitation stage, during which the silica of solution is polymerizing to form colloidal particles, i.e., the primary silica particles also sometimes called the ultimate silica particles. In this stage, no appreciable number of colloidal silica particles have aggregated to form precipitating particles. The end of this stage may be considered to extend to a point at which the x value lies in the range of 4.2 to 5.3 (depending on the conditions present), or may be taken at the point where a Tyndall effect appears, which usually occurs between x values M42 and 5.3, but can occur at as high an x value as 7.0 or more under certain combinations of conditions.

The Tyndall effect concerned of course is that defined in J. Thewliss Encyclopaedic Dictionary of Physics, Pergamon Press, 1962, as follows:

Tyndall Effect. The scattering of light by very small particles, the scattered light being predominantly blue."

This authority further states that:

This phenomenon and its dependence on the size of the scattering particles was first investigated by Tyndall. The scattered intensity is proportional to the square of the volume of the particle and proportional to (l/A). Thus the scattering for light at the blue end of the spectrum is about ten times as great as for light at the red end."

Following the appearance of the Tyndall effect in the known processes, continuation of the acidulation causes progressive precipitation of the silica pigment. When the Tyndall effect occurs between x values of 4.2 and 5.3, usually nearly 10 percent of the silica is precipitated by acidulation to an x value of about 6.4 (or higher, depending on conditions present), and the precipitation of the silica pigment is substantially complete when percent of the stiochiometric quantity of acidulating agent has been added, or when at least percent of the silica has precipitated, at which point x has a value of about 10 or more (which value may also vary with the conditions present, e. g. may be lowered to 40-50 percent of the stoichiometric amount when substantial quantities of non-acidulating electrolyte are present). Also depending on the conditions present, the extent of flocculation of the precipitate may vary.

After the precipitation has been completed, usually at least the balance of the stoichiometric quantity of carbon dioxide to convert the Na 0 of the sodium silicate to Na CO and generally an amount somewhat in excess thereof, is added.

It has heretofore been proposed in my aforesaid joint applications to use different rates of acidulation or differeht alkali metal ion concentrations in the several stages mentioned, i.e.

Stage 1: while x is rising to about the Tyndall effect value, or to an attained value of between 4.2 and 5.3.

Stage 2: while it is rising from the aforesaid value to a value at which about 10 percent of the silica has precipitated, or a value of about 6.4.

Stage 3a: while x is rising therefrom to a value of 10 or more,

Stage 3b: when the value ofx has risen above 10,

and it has been proposed in my copending sole application Ser. No. 458,480 filed May 24, 1965 (U.S. Pat. No. 3,307,906, issued Mar. 7, 1967) to effect different dilutions of the aqueous alkali metal silicate during different stages of the acidulation, and it is to be understood that such proposals and proposals of other copending applications for patent on sole or joint inventions of the present applicant, may be employed with, and in certain instances form new combinations with, the new provisions of the present invention.

By the present invention, we have discovered that particular advantage is attained by a process for the precipitation of reinforcing silica pigment by the gradual acidulation of an aqueous solution of alkali metal silicate, especially sodium silicate, with the aid of carbon dioxide, particularly characterized in that the temperature at which the acidulation is effected during at least two of the said three stages of acidulation are varied relative to each other in predetermined manners.

In a first embodiment of the invention, the temperature of acidulation during the first and second of said stages may be maintained at a relatively low or intermediate level, and may be increased to a higher level at the beginning of said stage 3, e. g. beginning as soon as the commencement of precipitation is observed. By this embodiment it is possible to control the size of the primary particles formed in the first stage as well as the size or compaction of the colloidal aggregates thereof formed in the second stage, by employing the lower temperature of acidulation under predetermined conditions, while controlling the flocculation and rate of separation of the precipitate by an altered temperature while the principal part of the precipitation is occurring.

In a second embodiment of the invention, the procedure may involve acidulation at relatively low or intermediate temperature during the second stage and relatively high temperature acidulation during the third stage, and may also involve relatively high temperature acidulation during the first stage. By this embodiment it is possible to control the size of the primary particles formed in the first stage, as well as the size or compaction of the flocs precipitated in the third stage, relative to the size or compaction of the colloidal aggregates developed during the second stage, and in this and other embodiments involving reduction in temperature one may find it advantageous to effect the cooling between the stages involved concurrently with dilution or aging procedures described in copending applications of the present inventor as may also be done while raising the temperature.

In a third embodiment of the invention a relatively low or intermediate temperature of acidulation may be employed in the second and third stages, and a higher temperature of acidulation in the first stage. By this procedure the size of the primary particles may be increased relative to the sizes and compactions of the colloidal aggregates and flocs thereof.

Ina fourth embodiment, the higher temperatures may be employed in the second and third stages of acidulation, with the low or intermediate temperatures in the first stage. By this procedure the size of the primary particles may be reduced relative to the sizes and compactions of the colloidal aggregates and flocs thereof.

In a fifth embodiment of the invention, a higher temperature of acidulation may be employed in the second stage of the acidulation, with low or intermediate temperatures employed in the first and third stages. By this procedure the size and compaction of the colloidal aggregates may be varied relative to the size of the primary particles and relative to the size and compaction of the flocs produced.

In a sixth embodiment of the invention the higher temperatures may be employed in the first and second stages with the low or intermediate temperature employed in the third stage. By this embodiment the size of the primary particles and the size and compactions of the network particles are controlled relative to the size and compaction of the flocs obtained.

In modifications of each of these embodiments the average temperature in the 3b portion of the third stage may be maintained at either the high temperature value or at the intermediate or low temperature value, with consequent effect on the characteristics of the silica product.

In similar embodiments wherein electrolyte is introduced during or prior to the first stage, the low temperatures, rather than intermediate temperatures, may be used to better advantage.

In short, we have found that by applications of the present invention we can vary the size of the ultimate or primary particles relative to the size and compaction of the network aggregates thereof constituting the pigment particles, independently, and that by other applications of the invention we can vary the size and compaction of the flocs of network aggregates relative to the size of the network aggregates or pigment particles themselves, thus to facilitate filtration or prepare flocs well adapted for dispersion of the silica pigment to the extent required in the situs of use thereof.

In preferred species of the aforesaid embodiments: the rate of feeding of the carbon dioxide during the first stage and/or the second stage may be regulated to require a time (depending on the conditions present) of at least 30 minutes and not over 300 minutes; the high and the low or intermediate temperatures may be selected in the liquid range of water, i. e. from about 1C. to about 100C. at atmospheric pressure, or higher under higher pressurespreferably the higher temperature range being about il4C.; the intermediate range about 60il0C. and the low temperature range about 25: 24C. different ones of these temperaturesdiffering by at least 10C., and preferably by at least about 20C. -being used during selected stages of the precipitation process, and when desired the temperature change may be carried out gradually throughout part or all of the selected acidulation stage or stages; the concentration of the aqueous alkali metal silicate is maintained in the range of 0.1 to 1.8, more preferably 0.5 to 1.3 moles of SiO per liter during all or selected stages of the precipitation process; controlled agitation may be maintained during all or selected stages of the precipitation process; the aqueous alkali metal silicate may be maintained essentially free of quantities of metal salt other than that resulting from the acidulation of the alkali metal silicate or alkali metal salts may be added as electrolyte; and the rates of acidulation during the first and second acidulation periods may be relatively adjusted'to aid in controlling the relative sizes of the primary particles, the network particles, and the pigment flocs.

After the flocs of precipitated silica pigment have been formed they may be recovered from the mother liquor in any suitable or preferred manner, e.g. by centrifuging, filtering, etc., and the silica pigment may be removed as wet cake or otherwise, and may be used per se, or be subjected to after-treatments appropriate for their intended use.

The carbon dioxide gas employed in this invention may be full strength or may be diluted with air or other inert gases, e.g. such as the dilute carbon dioxide gas produced by the combustion of hydrocarbons such as propane or butane, --see for example, copending applications Ser. No. 458,132 filed May 24, 1965 (US. Pat.

No. 3,372,046, issued Mar. 5, 1968). It may be fed at constant rate or at somewhat varied rates during the respective acidulation periods, and while constant or substantially constant rates are preferred for uniformity of procedure and to facilitate process control, variations of course are permissible which essentially afford an average rate of the order of that referred to and which do not so far depart therefrom as to materially affect the result obtained.

The process of the invention may be conducted in a batchwise or stepwise manner, or continuously, depending on available equipment. Suitable apparatus, for example, is set forth in copending joint application Ser. No. 142,668 (now U.S. Pat. No. 3,256,068), in which, for example, the present invention can be practiced as a continuous process wherein the acidulation steps are applied to moieties of the alkali-metal silicate solution in a series of zones of differently selected temperatures.

In the examples herein, certain after-treatments are employed in each of the examples of the respective series set out to exemplify the invention and its advantages, but the particular after-treatments are not limiting of the invention claimed herein, and the novel ones thereof are claimed in other applications.

The silica product aswet slurry or filter cake may be masterbatched with latices of natural or synthetic elastomers and/or plastomers.

The novel features and combinations of the invention are set forth in the claims appended hereto, but the practice of the invention itself will be more precisely understood by reference to the following specific examples embodying the same, which are to be considered as illustrative and not restrictive of the invention.

EXAMPLES The examples set forth herein were carried out in the following manner:

To a precipitator vessel equipped with an agitator was added liters of 41 Be aqueous solution containing moles sodium silicate of the composition represented by Na 0/(SiO and 63 liters of water.

The temperature of the sodium silicate solution was adjusted to the selected temperature level for the first acidification stage and then prior to the second and/or third stage of acidulation adjusted to another selected temperature level where applicable, as shown in Tables land 11.

The acidulating agent was carbon dioxide and it was fed into the sodium silicate solution at relative constant rates throughout each of the acidulation periods to most clearly demonstrate the effects of the present invention, unaffected by variations of other factors contemplated in the more general applications of the invention above described.

The details as to the conditions pertaining to the several stages of the acidulation in the comparative examples (Examples 1, 5 and 6) and in the examples of the invention (Examples 2-4 and 7-9) are given in Tables l and 11:

TABLE 1 Example 1 No. (comp) 2 3 4 Run No. 60 237 228 236 Acidulation Stage 1: Temperature- Initial (C.) 60 80 80 -Final (C.) 80 6O 80 80 Time-Total (min.) 165 210 180 150 CO, Flow meter rating 4 4 4 4 Acidulation- Initial (36) 0 0 0 0 -Final (96) 28 42.5 36 21 x-value-lnitial 3.22 3.22 3.22 3.22 -Final 4.5 4.8 5.0 4.1 Stage 2: Temperaturelnitial (C.) 80 60-80 80-60" 80 -Final (C.) 80 120 60 80 Time-Total (min.) 135 30 260 150 CO, Flow meter rating 4 4 4 4 Acidulation- Initial (9b) 28 42.5 36 I 21 -Final (36) 51 67.5 79.5 52.3 x-value-lnitial 4.5 4.8 5.0 4.1 -Final 6.8 9.9 15.7 6.7 Stage 3: Temperaturelnitial ("C.) 80 80 60 80-60" -Final (C.) 80 80 60 60 Time-Total (min.) 375 300 250 345 CO, Flow meter rating 4 4 4 4 Acidulation- 1nitial(%) 51 67.5 79.5 52.3 -Final (36) I15 119 120.3 125 1/ Tyndall point 2/ precipitation occurring 3/ heating time 4 minutes 4/ cooling time 6 minutes Table 11 Example 5 6 No. (comp) (comp) 7 8 9 Run No. 247 191 231 223 233 Acidulation Stage 1: Temperature 1nitial(C.) 60 80 60 80 80 Final(C.) 60 80 60 80 80 Time- Total (min.) 102 88 90 60 CO, Flow meter rating 12 12 12 12 12 Acidulation- [nitial(%) 0 O 0 0 0 Final(%) 50 41.6 49 39 38 x-value Initial 3.22 3.22 3.22 3.22 3.22 final 6.4 5.5 6.3 5.3 5.2 Stage 2: Temperature 1nitial(C.) 60 80 60-80 8060 80 final(C.) 60 80 80 60 80 Time- Total (min.) 48 39 30 30 40 CO Flow meter rating 12 12 12 12 12 Acidulationlnitial(%) 50 41.6 49 39 38 final(%) 76 60 65 62.5 60 x-value initial 6.4 5.5 6.3 5.3 5.2 final 13.4 8.0 9.2 8.6 8.0 Stage 3: Temperature initial(C.) 60 80 80 60 80-60 final(C.) 6O 80 80 6O 60 Time Total (min.) 90 128 120 CO; Flow meter Rating 12 12 12 12 12 Acidulation initial(%) 76 60 65 62.5 60 final(%) 124 122 141 125 Tyndall point precipitation occurring heating time 4 minutes cooling time 6 minutes The silica pigment precipitates were filtered and washed until soluble salts were less than 1 percent; and for acidic salt after-treated samples a portion of each was treated with l percent aluminum sulphate until and 3 (Example 2) gave harder stocks and better tensile values, making said stocks better suited for suspension members not subjected to severe dynamic loading.

the pH reached 4.0; and for the acid after-treated sam- 5 2, se f he relatively low intermediate temperaples a portion of each was acidified with sulfuric acid to tures i Stages 2 d 3 d h i i l hi h a pH of 4.0. Each of the treated samples was filtered; perature i St 1 (E l 3), a e to k of dried overnight at 105C; and micropulverized, yieldaugmented il th d l d t l ing Silica pigmentsincreased hardness, well adapted for mechanical The silica pigment materials designated in Tables [A goods as i i i h d f tires and as the acidic Salt and acid'treated 3. use of the relatively low intermediate temperature T) Samples of Examples 1 through 9 were each in Stage 3, and the relatively high temperature in pounded with a butadiene-styrene type elastomer Stages 1 d 2 (Example 4), gave stocks of accordmg to the compoundmg f P set stantially augmented tensile strength, with essenforth in Table III hereof (novel features of which are n no incl-gage in hardness and with greatly Clamed copendmg apphcat'on 480,151 proved heat build-up characteristics, rendering the stock especially suitable for goods subjected to Table III prolonged dynamic stress, such as tires.

(ev i Furthermore, this table shows that these significant Compounding Ingredients t, parts Butadienwtyrene copolymer(SBR 1502) m0 changes in characteristics are effected with only a Silica pigmentmaterial 50 20 C. difference in the temperatures employed at the Amm'dam(AnFox'damzz46) several stages. When the differences in temperatures 2,2-methylene-bis (4-methyl-6- o o t.butylphenol) 2 are increased to 40 C., or even 60 C., the effects of the Carbon black E 2 invention are even more pronounced. Paracoumarone-indene resin(Cumar RH) l0 Magnesia 4 Tables II and [IA (Examples 5-9) show that at a rela- Zinc oxide l tively rapid rate of acidulation throughout, as com- 'gf gz 'g fig 0J5 pared to the use of the relatively low intermediate tem- N,N-di-o-tolylguanidine (DOTG) 1.5 perature throughout (comparative Example 5 Sulfur 3 Modified pmhafic hydride 0.75 l. the use of the relatively low interme diate tempera (Retarder PD) ture in the 1st stage only, with the higher tempera- Trielhamlami"? 1 tures in the second and third stages (Example 7) ave a SKO k h in b t ti ii t dt Carbon black optional and at2part level no appreciable efiecton vul- 0 g an y augmen e canizate properties. sile strength with only slight increase in hardness,

again affording an advantage in the case of rela- These compounds were aged overnight, re-milled tively rigid suspension members; and cured for l20 minutes at 287F. 2. the use of the relatively low intermediate tempera- The physical test data for the respective vulcanizates ture in the second and third stages and of the relacontaining the after treated samples of the silica pigtively higher temperature in the first stage (Examment examples of Tables I and ll, is set forth in Tables 40 ple 8) gave a stock having not only an increased IA and [IA thereof, respectively: tensile strength but also a decreased hardness, and

V V TAELE rar-Fss'in m rli Hard- After ness 300% 500% Ult. Eloi1g., Goodrich treat- (Shore modulus modulus tensile (pcrflex. (A H, Example No. merit A) (p.s.i.) (p.s.i.) (p.s.i.) cent) C.)

1 (Comp.) A-S-T 66 630 1,550 3,410 1 (Comp) as 915 2,100 3,150 2 s4 1, 345 3, 135 4, 655

TABLE llA thus better suited for uses requiring these charac- T's't fiat-('1 teristics;

500% I 3. the use of the relatively low intermediate temperaaf ter 300 u t. exampeathardness modulus modulus tensile elong. ture m the third Stage only with the relat'vely hlgh le No. me nt (Shore A) (psi) (psi) (psi) (96) temperature in the first and second stages (Exam- 5 (comp) T 83 545 3090 3625 555 ple 9), gave a stock of substantially increased ten 6 sile strength and which also has a relatively p) T 75 1235 3070 reduced hardness, adapting it especially for use 7 A- T 85 I380 3250 4495 590 T 74 so 2505 40] 5 640 where this combination of characteristics is desira- 9 A- T 72 960 2385 4225 660 big Tables I and IA show that at a slow rate of acidulation throughout (Examples 1, 2, 3 and 4), as compared to use of the higher temperatures throughout (Example 1 1. use of the relatively low intermediate temperature in Stage 1 and the higher temperature in Stages 2 Still referring to Tables II and "A, it will be seen that at the relatively rapid rate of acidulation throughout, as compared to the use of the relatively high temperature throughout (comparative Example 6):

l. the use of the temperature combination of Example 7 gave a stock of substantially increased tensile strength and hardness;

3. the use of the temperature combination f Example 9 gave a stock of still further increased tensile strength and somewhat reduced hardness;

thus in each instance modifying the characteristics of the vulcanizates in respects desirable in different fields of use.

While there have been described herein what are at present considered preferred embodiments of the invention, it will be obvious to those skilled in the art that modifications and changes may be made therein without departing from the essence of the invention. It is therefor understood that the exemplary embodiments are illustrative and not restrictive of the invention, the scope of which is defined in the appended claims, and that all modifications that come within the meaning and range of equivalents of the claims are intended to be included therein.

We claim:

1. A process for the production of silica pigment which comprises a. maintaining an aqueous solution of alkali metal silicate at a first average temperature within the liquid range of water during a first stage of acidulation while feeding carbon dioxide into the solution in an amount sufficient to form primary silica particles in colloidal suspension in the solution and to provide the appearance of a Tyndall effect in the solution, the time span from the commencing of the feeding of carbon dioxide until the appearance of the Tyndall effect being 30 to 300 minutes,

. maintaining the composition produced by step (a) at a second, lower average temperature within the liquid range of water during a second stage of acidulation while continuing the feeding of carbon dioxide into the composition, said second stage of acidulation beginning with the appearance of the Tyndall effect and ending when sufficient carbon dioxide has been fed to effect precipitation as pigment of about 10 percent of the silica content of the composition, said second average temperature being at least 10 degrees Centigrade lower than said first average temperature, and the duration of said second stage being about 30 to 300 minutes,

0. continuing the precipitation of the silica by continuing the feeding of carbon dioxide into the composition produced by step (b) until at least 90 percent of the silica has precipitated as pigment, while maintaining the temperature of the composition within the liquid range of water,

. continuing the feeding of carbon dioxide into the composition produced by step (0) until at least enough thereof has been fed to convert substantially all of the Na O content of the composition to Na CO and e. recovering the precipitated silica pigment from the mother liquor.

2. The process of claim 1 wherein the alkali metal silicate is sodium silicate and the aqueous solution of sodium silicate in step (a), prior to being contacted with the carbon dioxide, contains a weight ratio of Si0 to Na 0 of less than 3.8 to l.

3. The process of claim 1 wherein the average temperature of the solution in step (a) is maintained within the range of about 71 to 99C.

4. The process of claim 1 wherein the average temperature of the composition in step (b) is maintained within the range of about 1 to C.

5. The process of claim 1, wherein in step (e) the pigment is removed as wet cake.

6. A process for the production of silica pigment which comprises a. maintaining an aqueous solution of alkali metal silicate at a first average temperature within the liquid range of water during a first stage of acidulation while feeding carbon dioxide into the solution in an amount sufficient to form primary silica particles in colloidal suspension in the solution and to provide the appearance of a Tyndall effect in the solution, the time span from the commencing of the feeding of carbon dioxide until the appearance of the Tyndall effect being 30 300 minutes,

. maintaining the composition produced by step (a) at a second, lower average temperature within the liquid range of water during a second stage of acidulation while continuing the feeding of carbon dioxide into the composition, said second stage of acidulation beginning with the appearance of the Tyndall effect and ending when sufficient carbon dioxide has been fed to effect precipitation as pigment of about 10 percent of the silica content of the composition, said second average temperature being at least about 20 degrees Centigrade lower than said first average temperature, and the duration of said second stage being about 30 to 300 minutes,

0. continuing the precipitation of the silica by continuing the feeding of carbon dioxide into the composition produced by step (b) until at least percent of the silica has precipitated as pigment, while maintaining the temperature of the composition within the liquid range of water,

. continuing the feeding of carbon dioxide into the composition produced by step (c) until at least enough thereof has been fed to convert substantially all of the Na 0 content of the composition to Na CO and e. recovering the precipitated silica pigment from the mother liquor.

7. The process of claim 1, wherein, to form a dry product, in step (e) the pigment recovered from the mother liquid is filtered, washed and dried. 

1. A process for the production of silica pigment which comprises a. maintaining an aqueous solution of alkali metal silicate at a first average temperature within the liquid range of water during a first stage of acidulation while feeding carbon dioxide into the solution in an amount sufficient to form primary silica particles in colloidal suspension in the solution and to provide the appearance of a Tyndall effect in the solution, the time span from the commencing of the feeding of carbon dioxide until the appearance of the Tyndall effect being 30 to 300 minutes, b. maintaining the composition produced by step (a) at a second, lower average temperature within the liquid range of water during a second stage of acidulation while continuing the feeding of carbon dioxide into the composition, said second stage of acidulation beginning with the appearance of the Tyndall effect and ending when sufficient carbon dioxide has been fed to effect precipitation as pigment of about 10 percent of the silica content of the composition, said second average temperature being at least 10 degrees Centigrade lower than said first average temperature, and the duration of said second stage being about 30 to 300 minutes, c. continuing the precipitation of the silica by continuing the feeding of carbon dioxide into the composition produced by step (b) until at least 90 percent of the silica has precipitated as pigment, while maintaining the temperature of the composition within the liquid range of water, d. continuing the feeding of carbon dioxide into the composition produced by step (c) until at least enough thereof has been fed to convert substantially all of the Na2O content of the composition to Na2CO3, and e. recovering the precipitated silica pigment from the mother liquor.
 2. The process of claim 1 wherein the alkali metal silicate is sodium silicate and the aqueous solution of sodium silicate in step (a), prior to being contacted with the carbon dioxide, contains a weight ratio of Si02 to Na20 of less than 3.8 to
 1. 3. The process of claim 1 wherein the average temperature of the solution in step (a) is maintained within the range of about 71* to 99* C.
 4. The process of claim 1 wherein the average temperature of the composition in step (b) Is maintained within the range of about 1* to 70* C.
 5. The process of claim 1, wherein in step (e) the pigment is removed as wet cake.
 6. A process for the production of silica pigment which comprises a. maintaining an aqueous solution of alkali metal silicate at a first average temperature within the liquid range of water during a first stage of acidulation while feeding carbon dioxide into the solution in an amount sufficient to form primary silica particles in colloidal suspension in the solution and to provide the appearance of a Tyndall effect in the solution, the time span from the commencing of the feeding of carbon dioxide until the appearance of the Tyndall effect being 30 300 minutes, b. maintaining the composition produced by step (a) at a second, lower average temperature within the liquid range of water during a second stage of acidulation while continuing the feeding of carbon dioxide into the composition, said second stage of acidulation beginning with the appearance of the Tyndall effect and ending when sufficient carbon dioxide has been fed to effect precipitation as pigment of about 10 percent of the silica content of the composition, said second average temperature being at least about 20 degrees Centigrade lower than said first average temperature, and the duration of said second stage being about 30 to 300 minutes, c. continuing the precipitation of the silica by continuing the feeding of carbon dioxide into the composition produced by step (b) until at least 90 percent of the silica has precipitated as pigment, while maintaining the temperature of the composition within the liquid range of water, d. continuing the feeding of carbon dioxide into the composition produced by step (c) until at least enough thereof has been fed to convert substantially all of the Na20 content of the composition to Na2CO3, and e. recovering the precipitated silica pigment from the mother liquor. 